缺陷UiO-66催化剂在温和条件下实现甲烷高选择性氧化制乙酸

doi:10.1016/S1872-2067(26)65127-3

催化学报 ›› 2026, Vol. 88: 356-368.DOI: 10.1016/S1872-2067(26)65127-3

缺陷UiO-66催化剂在温和条件下实现甲烷高选择性氧化制乙酸

魏耀文^a, 王建伟^a, 郭皓^a^,^*(), 班涛^a, 岳玉峰^a, 胡地^a^,^*(), 黄海保^a^,^b^,^*()

^a 新疆大学化工学院, 新疆煤炭清洁转化与化工过程重点实验室, 新疆乌鲁木齐 830046
^b 中山大学环境科学与工程学院, 广东广州 510275

收稿日期:2025-11-19 接受日期:2026-02-13 出版日期:2026-09-18 发布日期:2026-09-05
通讯作者: *电子信箱: guohao@xju.edu.cn (郭皓),
hudi13@126.com (胡地),
seabao8@gmail.com (黄海保).
基金资助:
国家重点研发计划(2024YFC3713500);新疆维吾尔族自治区重大科技专项(2024A03012);国家自然科学基金(22276223);新疆维吾尔族自治区重点研发计划(2022B03029-3);新疆维吾尔自治区人才项目“天池博士”计划(TCBS202013);新疆维吾尔族自治区自然科学基金(2023D01C170)

Highly selective oxidation of methane to acetic acid enabled by deficient UiO-66 under mild conditions

Yaowen Wei^a, Jianwei Wang^a, Hao Guo^a^,^*(), Tao Ban^a, Yufeng Yue^a, Di Hu^a^,^*(), Haibao Huang^a^,^b^,^*()

^a Xinjiang Key Laboratory of Coal Clean Conversion & Chemical Engineering Process, School of Chemical Engineering and Technology, Xinjiang University, Urumqi 830046, Xinjiang, China
^b School of Environmental Science and Engineering, Sun Yat-sen University, Guangzhou 510275, Guangdong, China

Received:2025-11-19 Accepted:2026-02-13 Online:2026-09-18 Published:2026-09-05
Supported by:
The National Key Research and Development Program of China(2024YFC3713500);The Major Science and Technology Projects of Xinjiang(2024A03012);The National Natural Science Foundation of China(22276223);The support of the Key Research and Development Plan of Xinjiang(2022B03029-3);The “Tianchi Talents” Introduction Plan(TCBS202013);The Natural Science Foundation of Xinjiang Uygur Autonomous Region(2023D01C170)

摘要/Abstract

摘要：

在温室效应持续加剧的形势下, 甲烷作为高效温室气体, 其排放治理与资源化利用已成为减排领域的关键议题. 与此同时, 甲烷又是储量丰富的清洁碳源, 若能实现高选择性催化转化, 可在“控排放-增价值”之间建立协同路径. 甲烷分子惰性源于高键能C-H键, 使得温和条件下的选择性活化与定向转化长期受限. 相较于甲烷制合成气及甲醇等C1路线, 直接生成乙酸等C2含氧化学品兼具更高的经济附加值与潜在的过程减碳优势. 然而, 该过程面临双重瓶颈: 其一, 活化初始C-H键需要高效且可控的活性氧物种; 其二, 后续C-C偶联与氧化深度难以协同调控, 易导致过氧化生成CO₂或形成多种副产物. 因此, 构建具备可调微环境、能够同时调控氧化剂活化与关键中间体稳定的异相催化体系, 是实现甲烷温和选择性氧化制乙酸的核心科学问题.
本工作以UiO-66为模型MOF, 提出“配体缺陷诱导的本征Zr活性中心重构”策略: 通过在合成过程中引入三氟乙酸(TFA)竞争配位, 调控“缺失配体”缺陷, 暴露配位不饱和Zr⁴⁺位点, 从而在无需外加异金属的条件下建立明确的本征活性中心. 结构表征表明, 适量TFA调控可在保持UiO-66骨架衍射特征的同时引入可控缺陷; 其中, UiO-66-0.3T呈现更高孔结构可及性与缺陷有序化特征, 比表面积达到1043.3 m² g^-1, 并由热重定量得到Zr₆节点配位缺失数约为4.98. X-射线光电子能谱与电子结构分析显示, 缺陷调控引发Zr位点电子结构重构, 表现为Zr 3d相关d带中心上移, 这有利于增强对氧化剂与甲烷的界面电子耦合. 在以H₂O₂为氧化剂的甲烷选择氧化反应中, TFA调控后的UiO-66-XT整体优于本征UiO-66, 并呈现随缺陷程度变化的“火山型”性能相关性. 在最佳条件下(150 °C, 6 h, 30 bar CH₄, 10 mL 5 wt% H₂O₂, 30 mg催化剂), UiO-66-0.3T实现含氧产物总产率1971 μmol g_cat.^-1, 其中乙酸产率1691 μmol g_cat.^-1, 乙酸选择性高达84%; 催化剂在至少5次循环中保持稳定. 对温度与H₂O₂浓度的系统考察进一步表明, 升温可促进乙酸生成, 但超过150 °C后过氧化趋势增强, 导致CO₂增多且选择性下降; H₂O₂浓度在5 wt%附近达到最优, 过量氧化剂会导致含氧产物深度氧化. 通过电子顺磁共振(EPR), 原位漫反射红外光谱(DRIFTS)及密度泛函理论(DFT)计算阐明了反应机理: EPR结果直接观察到催化剂在H₂O₂体系中高效生成•OH, 并在引入CH₄后出现•CH₃信号, 说明缺陷Zr位点促进H₂O₂活化并触发甲烷C-H键断裂; 原位DRIFTS检测到*OH, *COOH与*CH₃COOH等关键表面物种的生成与积累, 表明反应主要沿“缺陷位点上活性氧供给-甲烷定向活化-COOH稳定-C-C偶联”路径进行; DFT计算给出UiO-66-0.3T对CH₄与H₂O₂的吸附能分别为-0.63与-2.94 eV(UiO-66为-0.54与-1.89 eV), 并通过电荷重分布与轨道耦合增强解释了其更高的H₂O₂分解与甲烷活化能力. 由此可见, 缺陷诱导的电子结构重构与位点可及性提升, 协同调控了活性氧生成, 甲烷活化与C-C偶联, 进而显著提升乙酸选择性与产率.
综上, 本研究通过缺陷工程激活MOF骨架中金属团簇的本征催化潜力, 在温和条件下实现甲烷向C2含氧化学品的定向转化. 未来可围绕缺陷类型及空间分布的精准调控, 反应微环境与自由基通量的定量关联及连续化反应体系适配开展深入研究, 为温和条件下甲烷高值利用催化剂的设计提供可推广范式.

关键词: 甲烷, 选择性氧化, 乙酸, UiO-66催化剂, 缺陷工程

Abstract:

The direct conversion of methane (CH₄) into higher-value C2 products is essential for the green and efficient conversion of clean energy. However, this conversion process faces significant challenges due to the difficulty in activating methane's C-H bonds and the complexity of controlling C-C coupling reactions. Herein, we design and construct the unsaturated metal Zr⁴⁺ site by introducing ligand defects in UiO-66 through treatment with trifluoroacetic acid (TFA), which enables the direct oxidation of methane to acetic acid using H₂O₂ under mild conditions. Remarkably, a volcano-shaped correlation was observed between the degree of ligand defects in UiO-66 and acetic acid selectivity. Under optimal conditions (150 °C), the catalyst achieved an outstanding acetic acid selectivity of 84% with a high yield of 1691 μmol·g_cat.^-1. Notably, the catalyst exhibited exceptional stability, maintaining its performance over at least five consecutive reaction cycles. Through TFA modulation, the d-band center of the Zr 3d orbital in Zr⁴⁺ sites exposed by UiO-66 shifts upward. This promotes the decomposition of H₂O₂, thereby facilitating the formation and stabilization of highly reactive Zr-OH species, which enhances the activation of C-H bonds in CH₄. The resulting *CH₃ species is further oxidized by *OH species into *COOH species, which undergo stable C-C coupling at exposed Zr⁴⁺ sites to produce acetic acid. This work provides novel insights into the design of highly efficient catalysts for the direct conversion of methane into C2 oxygenates compounds under mild conditions.

Key words: Methane, Selective oxidation, Acetic acid, UiO-66 catalyst, Defect engineering

魏耀文, 王建伟, 郭皓, 班涛, 岳玉峰, 胡地, 黄海保. 缺陷UiO-66催化剂在温和条件下实现甲烷高选择性氧化制乙酸[J]. 催化学报, 2026, 88: 356-368.

Yaowen Wei, Jianwei Wang, Hao Guo, Tao Ban, Yufeng Yue, Di Hu, Haibao Huang. Highly selective oxidation of methane to acetic acid enabled by deficient UiO-66 under mild conditions[J]. Chinese Journal of Catalysis, 2026, 88: 356-368.

×
扫码分享

导出引用管理器 EndNote|Ris|BibTeX

链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(26)65127-3

https://www.cjcatal.com/CN/Y2026/V88/I9/356

图/表 7

Fig. 1. (a) Schematic presentation of the pristine UiO-66, defect induced via missing ligand UiO-66 structures and the synthesis of UiO-66-T. (b) TEM image of UiO-66. (c) TEM image of UiO-66-0.3T. (d) TEM image and the corresponding EDS elemental mapping for the distribution of O, C, and Zr elements for UiO-66-0.3T. (e) XRD patterns of as-prepared samples. (f) FT-IR spectra for UiO-66 and UiO-66-XT. (g) N2 adsorption-desorption isotherms for UiO-66 and UiO-66-XT.

Fig. 2. TG analyses for UiO-66 (a), UiO-66-0.1T (b), UiO-66-0.3T (c), and UiO-66-0.35T (d). (e) Schematic diagrams of the Zr6 node coordinated with 12 (theoretical value), 11, 10 and 9 ligands, respectively. (f) Raman spectra for UiO-66 and UiO-66-XT.

Fig. 3. (a) Adsorption of CO by UiO-66-0.3T at 298 K. (b) Desorption of CO at UiO-66-0.3T by N2 flowing at 373 K. (c) Adsorption of CO by UiO-66 at 298K. (d) Desorption of CO at UiO-66 by N2 flowing at 373 K.

Fig. 4. Product yield and acetic acid (CH3COOH) selectivity in the selective oxidation of CH4 with H2O2. (a) Catalytic performance of TFA-modulated UiO-66-XT with different TFA addition amounts. (b) Temperature-dependent CH4 oxidation performance over UiO-66-0.3T. (c) Influence of H?O? concentration on CH4 oxidation over UiO-66-0.3T. (d) Time-dependent CH4 oxidation over UiO-66-0.3T. (e) Recycling stability of UiO-66-0.3T. (f) Correlation between catalytic performance and defect density in UiO-66-XT. Unless otherwise specified, reactions were conducted with 10 mL of 5 wt% H2O2, 30 bar CH4, 30 mg catalyst at 150 °C for 6 h.

Fig. 5. The EPR spectra of DMPO-OH adducts produced by the interaction of UiO-66-0.3T (a) or UiO-66 and UiO-66-0.3T (b) with H2O2. (c) The EPR spectra of DMPO-OH and DMPO-CH3 adduct were observed in an aqueous solution in the presence of methane and UiO-66 or UiO-66-0.3T after in-situ irradiation. In-situ infrared spectra of UiO-66 (d) and UiO-66-0.3T (e).

Fig. 6. (a) Adsorption energy of CH4 on catalysts UiO-66 and UiO-66-0.3T. (b) Adsorption energy of H2O2 on catalysts UiO-66 and UiO-66-0.3T. The PDOS of the 1s state of H, 2p state of O/C and 3d state of Zr of CH4 dissociation on UiO-66 (c) and Ui0-66-0.3T (d). The PDOS of the 1s state of H, 2p state of O/C and 3d state of Zr of H2O2 dissociation on UiO-66 (e) and Ui0-66-0.3T (f). The differential charge maps of catalysts UiO-66 (g1) and UiO-66-0.3T (g2) during CH4 adsorption. The differential charge maps of catalysts UiO-66 (g3) and UiO-66-0.3T (g4) during H2O2 adsorption.

Fig. 7. The catalytic reaction path of UiO-66-0.3T for catalytic conversion of methane.

参考文献

[1]	L. Yang, H. J. Lin, Z. H. Fang, Y. H. Yang, X. H. Liu, G. Ouyang, Renew. Sustain. Energy Rev., 2023, 184, 113561.
[2]	Y. Tang, Y. Li, F. Feng Tao, Chem. Soc. Rev., 2022, 51, 376-423.
[3]	P. Kumar, T. A. Al-Attas, J. Hu, M. G. Kibria, ACS Nano, 2022, 16, 8557-8618.
[4]	H. R. Zhang, Y. Zhang, R. Huang, Z. W. Zhang, H. Zhou, Y. E. Wu, Y. H. Wang, F. Wu, J. Jiang, Y. Mao, L. Zheng, W. H. Zhong, L. Hu, S. C. Wang, X. K. Liu, T. Yao, Y. H. Ran, J. Cai, Z. Liu, Nat. Nanotechnol., 2025, 20, 1779-1786.
[5]	A. Caballero, P. J. Pérez, Chem. Soc. Rev., 2013, 42, 8809-8820.
[6]	K. Zheng, Y. Wu, J. Zhu, M. Wu, X. Jiao, L. Li, S. Wang, M. Fan, J. Hu, W. Yan, J. Zhu, Y. Sun, Y. Xie, J. Am. Chem. Soc., 2022, 144, 12357-12366.
[7]	A. A. Latimer, A. Kakekhani, A. R. Kulkarni, J. K. Nørskov, ACS Catal., 2018, 8, 6894-6907.
[8]	P. Tomkins, M. Ranocchiari, J. A. van Bokhoven, Acc. Chem. Res., 2017, 50, 418-425.
[9]	N. F. Dummer, D. J. Willock, Q. He, M. J. Howard, R. J. Lewis, G. Qi, S. H. Taylor, J. Xu, D. Bethell, C. J. Kiely, G. J. Hutchings, Chem. Rev., 2023, 123, 6359-6411.
[10]	Y. Zhao, Q. Gu, X. Sun, D. Wang, X. Gong, B. Yang, J. Xu, B. Peng, Y. Zhang, C. Pan, Y. Zhu, Y. Lou, Chem, 2024, 10, 3342-3363.
[11]	B. Yu, L. Cheng, J. Wu, B. Yang, H. Li, J. Xu, Y. Zhang, C. Pan, X.-M. Cao, Y. Zhu, Y. Lou, Energy Environ. Sci., 2024, 17, 8127-8139.
[12]	B. Yu, W. Li, X. Tang, L. Cheng, J. Zhang, S. Yang, F. Liu, J. Xu, Y. Zhang, C. Pan, X.-M. Cao, Y. Zhu, Y. Lou, Nat. Commun., 2025, 16, 9471.
[13]	W. Begum, M. Chauhan, R. Kalita, P. Gupta, N. Akhtar, N. Antil, R. Newar, K. Manna, ACS Catal., 2024, 14, 10427-10436.
[14]	J. Sui, M.-L. Gao, B. Qian, C. Liu, Y. Pan, Z. Meng, D. Yuan, H.-L. Jiang, Sci. Bull., 2023, 68, 1886-1893.
[15]	G. Q. Fang, J. N. Hu, L. C. Tian, J. X. Liang, J. Lin, L. Li, C. Zhu, X. D. Wang, Angew. Chem., Int. Ed., 2022, 61, e202205077.
[16]	N. Antil, M. Chauhan, N. Akhtar, R. Newar, W. Begum, J. Malik, K. Manna, ACS Catal., 2022, 12, 11159-11168.
[17]	N. Antil, M. Chauhan, N. Akhtar, R. Kalita, K. Manna, J. Am. Chem. Soc., 2023, 145, 6156-6165.
[18]	M. Xia, L. Qiu, Y. Li, T. Shen, Z. Sui, L. Feng, Q. Chen, Mater. Lett., 2022, 307, 131078.
[19]	G. C. Shearer, S. Chavan, S. Bordiga, S. Svelle, U. Olsbye, K. P. Lillerud, Chem. Mater., 2016, 28, 3749-3761.
[20]	Z. Fang, B. Bueken, D. E. De Vos, R. A. Fischer, Angew. Chem. Int. Ed., 2015, 54, 7234-7254.
[21]	L. Wang, X. Wen, J. Li, P. Zeng, Y. Song, H. Yu, Chem. Eng. J., 2021, 405, 126681.
[22]	J. Liu, K. Zhou, S. Ullah, J. Miao, H. Wang, T. Thonhauser, J. Li, Small, 2023, 19, 2304460.
[23]	M. Islamov, P. Boone, H. Babaei, A. J. H. McGaughey, C. E. Wilmer, Chem. Sci., 2023, 14, 6592-6600.
[24]	D. Yu, M. Wu, Q. Hu, L. Wang, C. Lv, L. Zhang, J. Hazard. Mater., 2019, 367, 456-464.
[25]	H. Hu, H. Zhang, Y. Chen, Y. Chen, L. Zhuang, H. Ou, Chem. Eng. J., 2019, 368, 273-284.
[26]	Q. Xie, Y. Li, Z. Lv, H. Zhou, X. Yang, J. Chen, H. Guo, Sci. Rep., 2017, 7, 3316.
[27]	V. V. Butova, O. A. Burachevskaia, N. L. Drenchev, A. A. Tereshchenko, K. I. Hadjiivanov, Nanomaterials, 2025, 15, 779.
[28]	Y. Yin, R. Lv, X. Li, L. Lv, W. Zhang, Appl. Catal. B, 2021, 299, 120685.
[29]	K. Chen, Q. Liu, Z. Qiu, H. Zhang, N. Gong, L. Zhu, J. Mater. Chem. A, 2024, 12, 23940-23947.
[30]	S. Y. Yoon, C. E. Choong, S.-N. Nam, C. M. Park, Y. Yoon, E. H. Choi, M. Jang, Chem. Eng. J., 2024, 490, 151217.
[31]	A. K. Kar, R. Sarkar, A. K. Manal, R. Kumar, S. Chakraborty, R. Ahuja, R. Srivastava, Appl. Catal. B, 2023, 325, 122385.
[32]	Y.-H. Li, M.-Y. Liu, Y.-W. Wei, C.-C. Wang, P. Wang, Environ. Sci.: Nano, 2023, 10, 672-682.
[33]	S. Fang, X. Zhu, X. Liu, J. Gu, W. Liu, D. Wang, W. Zhang, Y. Lin, J. Lu, S. Wei, Y. Li, T. Yao, Nat. Commun., 2020, 11, 1029.
[34]	C. Che, R. Li, T. Jia, W. Wang, D. Zeng, X. Qin, S. Xu, B. Jiang, W. Wang, H. Yang, L. Zhang, ChemCatChem, 2025, 17, e202402105.
[35]	B.-H. Chen, Z.-S. Chao, H. He, C. Huang, Y.-J. Liu, W.-J. Yi, X.-L. Wei, J.-F. An, Dalton Trans., 2016, 45, 2720-2739.
[36]	J. Liu, Y. Wei, R. Li, Y. Liu, H. Yu, X. Zhou, B. Wu, T. Lin, L. Zhong, Appl. Catal. B, 2024, 350, 123951.
[37]	S. Bai, F. Liu, B. Huang, F. Li, H. Lin, T. Wu, M. Sun, J. Wu, Q. Shao, Y. Xu, X. Huang, Nat. Commun., 2020, 11, 954.
[38]	W. Rachmady, M. A. Vannice, J. Catal., 2002, 207, 317-330.

缺陷UiO-66催化剂在温和条件下实现甲烷高选择性氧化制乙酸

Highly selective oxidation of methane to acetic acid enabled by deficient UiO-66 under mild conditions

RichHTML

PDF

Supporting Information

可视化

摘要/Abstract

引用本文

使用本文

扫码分享

图/表 7

参考文献

相关文章 15

编辑推荐

Metrics

[1]	张春雷, 谭涵予, 隋超阳, 冯莹, 陈心宇, 范晓强, 于学华, 赵震. MOF衍生多壳层Pd@Co₃O₄表面氧空位调控及催化甲烷高效燃烧[J]. 催化学报, 2026, 88(9): 492-505.
[2]	张心怡, 董威辰, 曹毅, 周彩霞, 郭家秀, 张海龙. Cu-KFI分子筛催化剂上甲烷直接转化高效连续合成甲醇[J]. 催化学报, 2026, 88(9): 369-381.
[3]	王松玲, 黄安华, 尹风星, 卢瑞祥, 刘文刚, 张云, 乔波涛. 原位合成双氧水用于甲烷高选择性氧化制甲醇[J]. 催化学报, 2026, 88(9): 347-355.
[4]	王阳, 贺雷, 唐帆, 李文翠, 何博文, 刘晰, 陈立桅, 王东琪, 申文杰, 陆安慧. 硼修饰缺电子镍催化无积碳甲烷干重整[J]. 催化学报, 2026, 87(8): 353-362.
[5]	马忠臣, 尹美怡, 徐润, 张荣俊, 兰天, 顾文丽, 陈国庆, 路勇. CeAlO₃镶嵌镍纳米颗粒抗积碳甲烷干重整催化剂[J]. 催化学报, 2026, 87(8): 363-375.
[6]	Shahla Karimi, Mehran Rezaei, 邓积光, 戴洪兴, Ali Rastegarpanah. 甲烷分解用贵金属基催化剂的最新进展: 性能、机理与优化[J]. 催化学报, 2026, 86(7): 9-48.
[7]	张淑敏, 许第发, 朱文君. 设计具有选择性氧反应活性的光催化剂用于太阳能驱动的甲烷偶联[J]. 催化学报, 2026, 86(7): 5-8.
[8]	闫小凤, 孟宇璇, 庹越凡, 薛耀, 杨千瑞, 罗正坤, 严逸珑, 林蒙, 赵宇飞, 孟宪光. Mn-Zn-O活性相促进MgO基氧化物的Ni-Co纳米金属析出用于光热甲烷干重整[J]. 催化学报, 2026, 85(6): 298-309.
[9]	顾宇, 张淑嘉, 徐铭潞, 闫昊, 周铭昊, 王磊, 施慧. 甲烷的脱氢芳构化及其与丙烷共芳构化: 反应机理、催化剂设计、积碳和过程强化[J]. 催化学报, 2026, 84(5): 25-60.
[10]	范海峰, 许狄, 曾婷, 侯国强, 李洋洋, 黄思懿, 徐艳飞, 王政, 高新华, 顾向奎, 定明月. 富电子Y₂O_3‒_x-Ni界面促进高效低温CO₂甲烷化反应[J]. 催化学报, 2026, 84(5): 200-213.
[11]	张宝龙, 孙彬, 刘兴朋, 刘文宇, 顾少楠, 周国伟. 缺陷工程促进TiO₂/Zn_0.5Cd_0.5S S型异质结电荷转移实现高效光催化析氢[J]. 催化学报, 2026, 84(5): 117-129.
[12]	郑芒, 李琪, 刘倩茜, 谷慧泉, 刘明阳, 刘琦, 蒋保江. 不对称双位点Bi-In氧桥用于高效光热催化二氧化碳甲烷化[J]. 催化学报, 2026, 83(4): 351-362.
[13]	武金玮, 陈俊妃, 张明康, 芮泽宝. Al₂O₃孤岛与Ir@Pt/TiO₂协同催化实现高活性耐硫甲烷氧化[J]. 催化学报, 2026, 83(4): 400-410.
[14]	饶成, 钱梦宇, 陶松芸, 王怀远, 何丹, 叶俊, 刘海, 杨向光, 张一波. 单原子Ni掺杂Pd/CeO₂增强甲烷催化燃烧性能: Pd⁴⁺和氧空位协同机制[J]. 催化学报, 2026, 83(4): 419-431.
[15]	李建荣, 张万鹏, 肖航, 田明姣, 何炽. 通过调节负载于MnO₂上的银初始状态促进乙酸乙酯低温深度氧化: 银纳米颗粒和离子的内在作用[J]. 催化学报, 2026, 83(4): 388-399.